CN101050171A - Method for producing unsaturated fatty acid - Google Patents
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- CN101050171A CN101050171A CNA2006100732289A CN200610073228A CN101050171A CN 101050171 A CN101050171 A CN 101050171A CN A2006100732289 A CNA2006100732289 A CN A2006100732289A CN 200610073228 A CN200610073228 A CN 200610073228A CN 101050171 A CN101050171 A CN 101050171A
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- C—CHEMISTRY; METALLURGY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/007—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids using organic solvents
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/14—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by isomerisation
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Abstract
Disclosed relates to a method for preparing unsaturated fatty acids and, more particularly, to a method for preparing unsaturated fatty acids in a high purity of at least 99% by isolating and purifying unsaturated fatty acids via a secondary nucleation mechanism using fatty acid-urea inclusion compounds.
Description
Technical field
The present invention relates to prepare the method for unsaturated fatty acids, more specifically, relate to the method for the highly purified unsaturated fatty acids of preparation at least 99%, this method is separated and purification of fatty acid by secondary nucleation mechanism with lipid acid-urea inclusion.
Background technology
Multiple animal and plant lipid acid, for example, vegetables oil such as Thistle oil, Trisun Oil R 80, olive wet goods and fish oil such as sardine oil contain the saturated and unsaturated fatty acids that food and medical purpose is had beneficial effect.Especially, the unsaturated fatty acids in fat and the oils lipid acid has caused attention, because it has various beneficial effects to food and medical purpose.
Typically, the method that fatty oil is transformed into lipid acid roughly is divided into enzymotherapy and organic synthesis method.The transformation efficiency of enzymotherapy has only 70% to 80%, is difficult to expect change into the effective lipid acid that food and medical purpose is had beneficial effect by enzymotherapy.Conjugated linolic acid is typical example.In addition, the transformation efficiency of organic synthesis method is about 98%, yet, separate and purification of fatty acid in difficulty also arouse attention because generation has the trans-9 of carcinogenic danger, anti-form-1 1 lipid acid in conversion.Carcinogenic substance is trans-9, and anti-form-1 1 lipid acid is inevitable by product, because the organic synthesis method focuses on the lipid acid isomerization under the high temperature, the cooling of aftertreatment technology is cared naught for.In addition, unreacted lipid acid residues in this step inevitably.Therefore, be necessary from animal and vegetable fatty oil, to separate and the unsaturated fatty acids of purification of high-purity, so that utilize the raw material of these unsaturated fatty acidss as food and medicine.The research that multiple method with these objectionable impuritiess of improvement removal is a purpose is still being proceeded.
The urea inclusion method is well-known as separating with the method for purifying unsaturated fatty acids from animal and vegetation fat and oils lipid acid.One of these methods, the alcohol-liquid cooling method that is used for dissolved fat acid simultaneously and urea has seen many documents (JAOCS, 59,117. about .118 (March nineteen eighty-two), Haagsma; Ratnayake, Fatsci.Technol.90,381 (1998), etc.).Yet, because this method of cooling can not be controlled the size of urea molecule group, urea and urea inclusion simultaneously with crystalline form deposition, have therefore weakened the efficient of urea sharp in cooling step, this causes the not removed shortcoming of unwanted lipid acid.Therefore, Chang Gui alcohol-liquid cooling method has been used to separation medium purity rather than highly purified unsaturated fatty acids.In addition, increase with the demand of these shortcomings of overcoming ordinary method reducing rate of cooling.
Yet the method that has been lowered according to rate of cooling still has some shortcomings, and process is slow, and becomes sour rapidly because unsaturated fatty acids is under the high temperature for a long time, thereby has reduced oxidation of fatty acids stability.Therefore, this method has been damaged the quality of product, can not be used for scale operation.
In order to overcome these shortcomings, Korean Patent Publication No. 10-2002-0042432 discloses a kind of method that is used to separate with purification of high-purity lipid acid, this method is implemented urea inclusion crystallisation step, then, optionally utilizes crystallisation by cooling or high performance liquid chromatography.It is possible utilizing this method economically, yet, can not provide a perfect high separation rate, because only control the behavior of urea molecule group by the cooling step of this method.In addition, can not avoid the precipitation of urea crystal, and the processing required time is elongated, because this method has also been used several steps such as crystallisation by cooling, high performance liquid chromatography except the crystallization of urea inclusion, this is the other shortcoming of ordinary method.
Therefore, the inventor has studied from fat and oils lipid acid and has prepared the method for high purity unsaturated fatty acids and finished the present invention, the present invention has strengthened oxidation of fatty acids stability by the time that the shortening unsaturated fatty acids is under the high temperature, only utilize urea inclusion crystallisation step, optionally separate and the acid of purifying desired fats, by using lipid acid-urea inclusion to control the behavior of urea molecule group and the urea crystal precipitation does not take place, obtain at least 99% highly purified unsaturated fatty acids thus through secondary nucleation mechanism.
Summary of the invention
Therefore, an object of the present invention is to provide a kind of method, separate and purification of fatty acid the highly purified unsaturated fatty acids of preparation at least 99% through secondary nucleation mechanism by using lipid acid-urea inclusion.
The method that the present invention prepares unsaturated fatty acids comprises the following steps: that (1) put into C with NaOH
1～C
5With dissolving fully, the reactant that adding fat and oils lipid acid and cooling are produced in gained solution is to be converted into lipid acid in the alcohol; (2) in ethanolic soln, add urea with dissolving fully, and in gained solution, be added in the middle lipid acid that obtains of step (1) to form lipid acid-urea inclusion; (3) stir ethanolic soln, urea and lipid acid with dissolving fully, cooling gained solution, simultaneously, the lipid acid-urea inclusion that is added in acquisition in the step (2) in the gained reactant is to obtain lipid acid.
The method for preparing unsaturated fatty acids of the present invention will be set forth in after this step.
In step (1), to the C of 1.0 weight fractions (weight fraction)
1～C
5The NaOH that adds 0.25 to 0.5 weight fraction in the alcohol is with dissolving fully.The temperature that keeps reactant adds the fat of 1.0 to 2.0 weight fractions and oils lipid acid and makes it under such high temperature isomerization one and half to two (1.5 to 2) hour within 170 ℃ to 180 ℃ in solution.Then, cool off the gained reactant down to stop isomerization steps at 50 ℃ to 60 ℃.By such cooling step, unreacted lipid acid might be converted into and be higher than 99% unsaturated fatty acids and make the carcinogenic risk material trans-9, the formation of anti-form-1 1 lipid acid minimizes.If implement the high speed method of cooling, just might suppress trans-9, the formation of anti-form-1 1 lipid acid, yet, can not further carry out of the conversion of unreacted lipid acid to unsaturated fatty acids.On the contrary,, just might realize of the fully conversion of unreacted lipid acid to unsaturated fatty acids if implement low speed method of cooling or controlled method of cooling, yet, just can not avoid owing to lasting heat production cause trans-9, the formation of anti-form-1 1 lipid acid.Therefore, be appreciated that such cooling conditions is most important factors to overcoming the problems referred to above.
Above-mentioned C
1～C
5Alcohol comprises methylene glycol, ethylene glycol, propylene glycol, butyleneglycol and pentanediol.Preferably, can use propylene glycol.
When the temperature of reactant reaches 50 ℃ to 60 ℃, in reactant, slowly add phosphoric acid the pH value is adjusted to 1.After leaving standstill with this understanding, remove the bottom of reactant and use distilled water wash top fatty-acid layer.Repeat this process two to three times with thorough removal impurity soluble in water.This step gained lipid acid contains 0.2% to 0.5% unreacted lipid acid and 1.0% or still less trans-9, anti-form-1 1 lipid acid.
Fat and oils lipid acid contain multiple animal and plant fatty oil, for example, and vegetables oil such as Thistle oil, Trisun Oil R 80, olive wet goods and fish oil such as sardines wet goods.
Gained lipid acid preferably has the unsaturated fatty acids of 10 to 30 carbon atoms and 1-6 key in the step (1), more preferably, comprise be selected from down the group at least a: Oleomyristic acid, Zoomeric acid, gamma-linolenic acid, alpha-linolenic acid, oleic acid, linolic acid, conjugated linolic acid, docosahexenoic acid (DHA) and timnodonic acid (EPA).
In step (2), under 25 ℃ to 30 ℃ temperature, the urea of 1.0 weight fractions and the ethanolic soln of 3.0 to 5.0 weight fractions are mixed to dissolving fully.Keep this temperature, step (1) the gained lipid acid that adds 0.2 to 0.4 weight fraction in solution is to form lipid acid-urea inclusion.Then, filtration and dry gained crystal are with the nucleus as following secondary nucleation mechanism.Here, the concentration of used ethanolic soln can be 60% to 80%, preferably, and 70% concentration.
In step (3), under 60 ℃ to 70 ℃, the ethanolic soln of 9.0 to 12.0 weight fractions, the urea of 3.0 to 4.0 weight parts and the lipid acid of 1.0 weight fractions are mixed to dissolving fully.Then, cool off this solution with 0.5 to 1.0 ℃/minute rate of cooling, under 45 ℃ to 50 ℃ the temperature in the step that wherein adds 0.01 to 0.05 weight fraction (2) gained fat-urea inclusion.Here, it would be desirable the maintenance crystalline form, not dissolved.Under the condition that crystal exists, cooling reactant and filtration under 10 ℃ to 15 ℃ temperature.Identify crystal and solution part with gas chromatographicanalyzer after, get the part that shows lipid acid-urea inclusion.Then, adding weight ratio to crystal (or solution part) is 1: 1 water and hexane, then, mixes to wherein adding small amount of hydrochloric acid, forms the hexane of fatty acids so at an upper portion thereof.Next, the hexane on removal top can obtain the concentration of fatty acid in 60% to 99% scope.Here, the concentration of used ethanolic soln can be 60% to 80%, and preferably, 70% concentration is as step (2).
If as second nucleus, result such as purity, the rate of recovery etc. of method are had tremendous influence without lipid acid-urea inclusion.That is, in this case, owing to need quite long induction time crystallizing out, precipitate under the temperature of urea crystal when being lower than use lipid acid-urea inclusion from the scintilla level.Therefore, the temperature difference between urea inclusion crystallization and the urea crystal precipitation about 5 ℃ with interior system in, if do not use lipid acid-urea inclusion as secondary nucleation, then the precipitation of urea crystal is inevitable.Therefore, use the secondary nucleation mechanism of lipid acid-urea inclusion can make the utilization ratio of resolving power, the rate of recovery and urea reach maximization among the present invention.
In addition, the present invention can be not having separation and purification of high-purity unsaturated fatty acids under the sedimentary situation of urea inclusion, even under high rate of cooling (that is, 0.5 to 1.0 ℃/minute).
According to the present invention, can use lipid acid-urea inclusion to separate highly purified unsaturated fatty acids with purifying at least 99% by secondary nucleation mechanism, this unsaturated fatty acids has the beneficial effect that is applied to food, makeup and medicine purpose.
The accompanying drawing summary
The schema of Fig. 1 has shown the method for preparing the high purity unsaturated fatty acids according to the present invention from fat and oils lipid acid;
Fig. 2 has shown the gas chromatograph analytical results (PA: Zoomeric acid of the conjugated linolic acid that obtains by the preferred embodiment of the invention; SA: stearic acid; OA: oleic acid; CLA (c9t11): suitable-9, anti--the 11-conjugated linolic acid; CLA (t10c12): trans-10, suitable-the 12-conjugated linolic acid; CLA (t9t11): anti--9, anti--the 11-conjugated linolic acid);
Fig. 3 has shown scanning electronic microscope (SEM) image with lipid acid-urea inclusion and urea among the present invention of SEM measurement;
Fig. 4 has shown X-ray diffraction (XRD) data with lipid acid-urea inclusion and urea among the present invention of XRD measurement.
Embodiment
Below, describe the preferred embodiments of the invention with reference to the accompanying drawings in detail.The invention is not restricted to following embodiment, have many variations within the spirit and scope of the present invention.It is in order more completely to explain the present invention to those skilled in the art that embodiment of the present invention are provided.
Embodiment 1: the preparation of conjugated linolic acid
1. the conversion of conjugated linolic acid
To temperature remain on add the 500ml propylene glycol in 175 ℃ the synthesis reactor after, if temperature is reduced to 130 ℃, in synthesis reactor, add 250g NaOH and dissolving fully.Next, stir gained solution and rise to 175 ℃ up to temperature.In solution, add 1kg Thistle oil (75% linolic acid) to carry out the conjugation isomerization reaction one and a half hours.Then, behind this solution of cooling under 50 ℃ the temperature, stop the conjugation isomerization reaction.When temperature is reduced to 50 ℃, in reactant, slowly add phosphoric acid the pH value is transferred to 1.After leaving standstill with this understanding, the bottom of removing reactant is also with the conjugated linolic acid layer in the distilled water wash top.Carry out this process two to three times with thorough removal impurity soluble in water.This step gained 952g conjugated linolic acid (95.2%) contains 0.5% or unreacted linolic acid still less and 0.8% or still less trans-9, anti-form-1 1 linolic acid.
Fig. 1 has described the method for preparing the high purity unsaturated fatty acids according to the present invention from fat and oils lipid acid in schema.Fig. 2 has shown the analytical results of the gas chromatograph of gained conjugated linolic acid in the step 1.
As shown in Figure 2, the conjugated linolic acid that transforms comprises 6.59% Zoomeric acid, 2.86% stearic acid, 14.20% oleic acid, 37.36% cis-9, anti-form-1 1 conjugated linolic acid, 38.91% anti-form-1 0, cis-12 conjugated linolic acid and 0.08% trans-9, anti-form-1 1 conjugated linolic acid.Therefore, it is trans-9 to be appreciated that the method for preparing unsaturated fatty acids of the present invention can minimize carcinogenic substance, the formation of anti-form-1 1 conjugated linolic acid.
2. prepare conjugated linolic acid-urea inclusion crystal
In 70% ethanolic soln of 9L, add 3kg urea and dissolving fully under 25 ℃ to 30 ℃ temperature.Keep this temperature, in gained solution, add in the 952g step 1 the gained conjugated linolic acid to form conjugated linolic acid-urea inclusion crystal.Next, this solution of filtration under diminished pressure and under 50 ℃ temperature the dried crystals part.Be used as nucleus in this crystal secondary nucleation mechanism below.With the figure of the SME among Fig. 3 and Fig. 4 and this step gained crystal of XRD DATA REASONING.
As shown in Figure 3, find that urea itself has rectangular shape (tetragonal system) and lipid acid-urea inclusion crystal has hexagonal configuration (crystallographic system).
In addition, according to powder diffraction studies joint committee (JCPDS) card, know that urea itself has rectangular shape, and lipid acid-urea inclusion crystal has hexagonal configuration.As shown in Figure 4, have hexagonal configuration, therefore be appreciated that to have formed this crystal in this step owing to find the lipid acid-urea inclusion crystal that obtains according to the present invention.
3. the preparation of conjugated linolic acid
In 12L 70% ethanolic soln, add 4kg urea and 1kg conjugated linolic acid and dissolving fully under 70 ℃.Then, with of the rate of cooling cooling of gained solution with 0.7 ℃/minute.When temperature is reduced to 50 ℃, in refrigerative solution, add the conjugated linolic acid-urea inclusion crystal that forms in the 200g step 2.Here, expectation be that crystal not exclusively melts and keeps its crystal shape.Under the condition that crystal exists, gained solution is cooled to 10 ℃ with 0.7 ℃/minute rate of cooling.Then, filtration under diminished pressure and collect crystal block section.When in gained solution, adding 5kg water, 2ml hexane and small amount of hydrochloric acid and stirring, formed the hexane that contains conjugated linolic acid at an upper portion thereof, obtain the spissated conjugated linolic acid of 930g (93.0%) by remove hexane from top thus.
The preparation of embodiment 2 gamma-linolenic acids
Substitute conjugated linolic acid with borage oil lipid acid (20% gamma-linolenic acid), with embodiment 1 in step 1 and 2 same modes obtain gamma-linolenic acid-urea inclusion crystal.
In 12L 70% ethanolic soln, add 4kg urea and 1kg borage oil lipid acid (20% gamma-linolenic acid) and dissolving fully under 70 ℃ temperature.Then, with of the rate of cooling cooling of gained solution with 0.7 ℃/minute.When temperature is reduced to 50 ℃, in refrigerative solution, add gamma-linolenic acid-urea inclusion crystal that 250g forms in above step.In the crystal existence and under the nonfused condition, reduce to 15 ℃ until temperature with 0.5 ℃/minute rate of cooling cooling gained solution.Then, filtration under diminished pressure and discard crystal block section.Then with the ethanol in the rotation vacuum-evaporation instrument evaporated filtrate.Add 1kg water, 0.5ml hexane and small amount of hydrochloric acid and stirring then in the gained solution, formed the hexane that contains gamma-linolenic acid at an upper portion thereof, when removing hexane, obtain the spissated conjugate linolenic acid of 170g (99.3%) thus from top.
The preparation of embodiment 3 docosahexenoic acids (DHA)
Conjugated linolic acid with in the step 1 and 2 in microbial fermentation breast (40%DHA) alternate embodiment 1 obtains DHA-urea inclusion crystal in the same way.
In 9L 70% ethanolic soln, add 3kg urea and 1kg microbial fermentation breast (40%DHA) and dissolving fully under 70 ℃ temperature.Then, with of the rate of cooling cooling of gained solution with 0.6 ℃/minute.When temperature is reduced to 50 ℃, in refrigerative solution, add the DHA-urea inclusion crystal of 200g gained in above step.Exist and under the nonfused condition, gained solution is reduced to 10 ℃ until temperature at crystal with 0.5 ℃/minute rate of cooling.Then, filtration under diminished pressure also discards crystal block section, then with the ethanol in the rotation vacuum-evaporation instrument evaporated filtrate.When in gained solution, adding 1kg water, 0.5ml hexane and small amount of hydrochloric acid and stirring, obtained to contain the hexane of DHA at an upper portion thereof then, therefore when removing hexane, obtained the spissated DHA of 150g (99.1%) from top.
EXPERIMENTAL EXAMPLE: fatty acid compositional analysis
Carry out following experiment to identify the purity of lipid acid of the present invention.
(Shimadzu cp 9001 Chrompack) analyzes respectively according to embodiment 2 and the gamma-linolenic acid of 3 preparations and the composition of DHA with gas chromatographicanalyzer.
As a comparative example, adopt gamma-linolenic acid (GLA) and the DHA for preparing according to disclosed method among the Korean Patent Publication No. 10-2002-42432.
The results are shown in table 1
[table 1]
| The present invention | Comparative example | ||||
| Method therefor | Embodiment 2 (GLA) | Embodiment 3 (DHA) | GLA | DHA | |
| Urea inclusion | Oleic acid: 0.0% linolic acid: 0.7% GLA:99.3% | DPA：0.9％ DHA： 99.1％ | Oleic acid: 0.6% linolic acid: 12.3% GLA:87.1% | Oleic acid: 6.3% linolic acid: 8.1% GLA:85.6% | |
| The crystallisation by cooling method | Do not use | Do not use | Linolic acid: 1.8% GLA:98.2% | GLA：1.5％ DPA：2.3％ DHA： 96.2％ | |
| Chromatography | Do not use | Do not use | Linolic acid: 0.9% GLA:99.1% | DPA：0.9％ DHA： 99.1％ | |
As shown in table 1, when using the urea inclusion method, obtain 99.3% and 99.1% gamma-linolenic acid and DHAs respectively according to the present invention, yet, be respectively 87.1% and 85.6% according to those of comparative example.As above describe in detail, can only just obtain the lipid acid of at least 99% purity with the urea inclusion method.But, in comparative example, have only the lipid acid that just can obtain at least 99% purity when using crystallisation by cooling method and chromatography simultaneously.
In ordinary method, because urea inclusion was slowly cooled more than one day, becomes sour and carry out rapidly, therefore, oxidation of fatty acids stability reduces.In order to improve becoming sour in the comparative example, lipid acid was added bit by bit in the mixture of ethanol and urea five to six hours.As a result, urea and urea inclusion are precipitated with the crystalline form simultaneously, so can not obtain highly purified lipid acid.Yet, because urea and urea inclusion coexist as in bunch (cluster), the behavior that method of the present invention is utilized oersted Wa Er slaking control urea molecule group is not with by crystallization but get back to atomic state, this theory relates to than macrocrystal from the relatively more reduced size crystalline growth of high-dissolvability of macrocrystal tool, and urea molecule adheres to lipid acid with formation lipid acid-urea inclusion like this.Here, adding weight ratio to lipid acid-urea inclusion is 1: 1 water and hexane and small amount of hydrochloric acid and stirring, thereby obtains highly purified lipid acid.
Therefore, according to the present invention, can only utilize the urea inclusion method and prepare high purity fatty acid without crystallisation by cooling method and chromatography.
The method for preparing unsaturated fatty acids among the present invention is controlled the behavior of urea molecule group by secondary nucleation mechanism with lipid acid-urea inclusion.Therefore, owing to method of the present invention is converted into urea inclusion fully with lipid acid and the urea crystal precipitation does not take place under high rate of cooling, so can in mass production, prepare unsaturated fatty acids by shortening the storage period under the high temperature.In addition, method of the present invention can sharply strengthen oxidation of fatty acids stability and selectivity.
Claims (10)
1. method for preparing unsaturated fatty acids, this method comprises the following steps:
(1) NaOH is put into C
1～C
5With dissolving fully, in gained solution, add fat and oils lipid acid and cool off resulting reactant in the alcohol to be converted into lipid acid;
(2) in ethanolic soln, add urea with dissolving fully, and in gained solution, be added in the middle lipid acid that obtains of step (1) to form lipid acid-urea inclusion; With
(3) stir described ethanolic soln, urea and lipid acid with dissolving fully, cooling gained solution, simultaneously, the lipid acid-urea inclusion that is added in acquisition in the step (2) in the gained reactant is to obtain lipid acid.
2. the method for preparing unsaturated fatty acids described in claim 1, wherein the alcohol in the step (1) is propylene glycol.
3. the method for preparing unsaturated fatty acids described in claim 1, the concentration of wherein said ethanolic soln is 60% to 80%.
4. the method for preparing unsaturated fatty acids described in claim 3, the concentration of wherein said ethanolic soln is 70%.
5. the method for preparing unsaturated fatty acids described in claim 1, wherein fat in the step (1) and oils lipid acid are animal or plant fat and oils lipid acid, comprise to be selected from down at least a of group: Thistle oil, Trisun Oil R 80, sweet oil and sardine oil.
6. the method for preparing unsaturated fatty acids described in claim 1, wherein said lipid acid comprise and are selected from down at least a of group: Oleomyristic acid, Zoomeric acid, gamma-linolenic acid, alpha-linolenic acid, oleic acid, linolic acid, conjugated linolic acid, docosahexenoic acid (DHA) and timnodonic acid (EPA).
7. the method for preparing unsaturated fatty acids described in claim 1, the NaOH that wherein adds 0.25 to 0.5 weight fraction in step (1) in the propylene glycol of 1.0 weight fractions is with dissolving fully, the fat of adding 1.0 to 2.0 weight fractions and oils lipid acid cool off the gained reactant with reaction under 50 ℃ to 60 ℃ temperature in solution.
8. the method for preparing unsaturated fatty acids described in claim 1 wherein comprises 0.2% to 0.5% unreacted lipid acid and 1.0% or still less trans-9, anti-form-1 1 lipid acid carrying out the described lipid acid in step (1) back.
9. the method for preparing unsaturated fatty acids described in claim 1, wherein in step (2) urea of 1.0 weight fractions is mixed with the ethanolic soln of 3.0 to 5.0 weight fractions with dissolving fully, the lipid acid that adds gained in the step (1) of 0.2 to 0.4 weight fraction in this solution is to form lipid acid-urea inclusion.
10. the method for preparing unsaturated fatty acids described in claim 1, wherein in step (3), the ethanolic soln of 9.0 to 12.0 weight fractions, the urea of 3.0 to 4.0 weight parts and the lipid acid of 1.0 weight fractions are stirred with dissolving fully, rate of cooling with 0.5 to 1.0 ℃/minute is cooled off this solution, and the lipid acid-urea inclusion of gained is to form lipid acid in the step that wherein adds 0.01 to 0.05 weight fraction (2).
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| KR1020050029829A KR100539357B1 (en) | 2005-04-11 | 2005-04-11 | A process for the preparation of unsaturated fatty acid |
| KR1020050029829 | 2005-04-11 |
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| KR20150028233A (en) | 2012-05-07 | 2015-03-13 | 옴테라 파마슈티칼스, 인크. | Compositions of statins and omega-3 fatty acids |
| CN104418726A (en) * | 2013-08-20 | 2015-03-18 | 陕西中鼎华盛农业发展有限公司 | Extraction method of [alpha]-linolenic acid |
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| CN107418737A (en) * | 2017-06-06 | 2017-12-01 | 江苏天晟药业股份有限公司 | The preparation method of unrighted acid in a kind of Silybum Marianum Gaertn Seed Oil |
| CN114853593B (en) * | 2022-05-12 | 2023-08-29 | 北京化工大学 | Method for extracting high-purity nervonic acid from acer truncatum oil |
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| JPS5231039A (en) * | 1975-09-02 | 1977-03-09 | Mitsui Petrochem Ind Ltd | Process for separation of m-cresol and p-cresol |
| JPS61297A (en) * | 1984-06-12 | 1986-01-06 | 日本油脂株式会社 | Manufacture of oleic acid |
| CH663951A5 (en) * | 1984-10-10 | 1988-01-29 | Nestle Sa | PROCESS FOR THE SELECTIVE ENRICHMENT OF POLYUNSATURATED FATTY ACIDS IN A MIXTURE CONTAINING ENRICHED FRACTION FATTY ACIDS AND COMPOSITIONS CONTAINING THE SAME. |
| JPH0662470B2 (en) * | 1986-08-25 | 1994-08-17 | 宇部興産株式会社 | Process for producing optically active hexa-2,4-diyne-1,6-diols |
| JPH0913072A (en) * | 1995-06-30 | 1997-01-14 | Sairaido Koryo Kk | Treating agent capable of partly saponifying and solidifying oil saponifiable and liquid at ordinary temperature like triglyceride and its production |
| US6015833A (en) * | 1998-03-17 | 2000-01-18 | Conlinco., Inc. | Conjugated linoleic acid compositions |
| KR20010008387A (en) * | 2000-11-30 | 2001-02-05 | 이성권 | Method for producing highly pure unsaturated fatty acid using crystallization |
| JP4213906B2 (en) * | 2002-04-12 | 2009-01-28 | 株式会社ヤクルト本社 | Method for producing conjugated linoleic acid |
| ATE509085T1 (en) * | 2005-02-04 | 2011-05-15 | Lipid Nutrition Bv | METHOD FOR PRODUCING FATTY ACIDS |
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2005
- 2005-04-11 KR KR1020050029829A patent/KR100539357B1/en not_active IP Right Cessation
-
2006
- 2006-03-24 US US11/388,416 patent/US20060229461A1/en not_active Abandoned
- 2006-04-05 CN CNA2006100732289A patent/CN101050171A/en active Pending
- 2006-04-06 JP JP2006105128A patent/JP2006291204A/en active Pending
- 2006-04-10 EP EP06007512A patent/EP1712609A1/en not_active Withdrawn
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353612B (en) * | 2008-08-22 | 2010-11-17 | 中南林业科技大学 | Method for enriching polyunsaturated fatty acid from pine caterpillar |
| CN102311882A (en) * | 2011-08-11 | 2012-01-11 | 青岛农业大学 | Extraction method for unsaturated fatty acid |
| CN102311882B (en) * | 2011-08-11 | 2012-12-26 | 青岛农业大学 | Extraction method for unsaturated fatty acid |
| CN103451025A (en) * | 2013-09-11 | 2013-12-18 | 江苏丘陵地区镇江农业科学研究所 | Method for separating unsaturated fatty acid |
| CN107090357A (en) * | 2017-06-21 | 2017-08-25 | 江苏中兴药业有限公司 | A kind of method of the extraction purification unrighted acid in Silybum Marianum Gaertn Seed Oil |
| CN108558644A (en) * | 2018-04-04 | 2018-09-21 | 赞宇科技集团股份有限公司 | A kind of production technology and device of industrial oleic acid |
| CN108558644B (en) * | 2018-04-04 | 2021-12-03 | 赞宇科技集团股份有限公司 | Production process and device of industrial oleic acid |
| CN108251221A (en) * | 2018-04-26 | 2018-07-06 | 孙万成 | A kind of method of purifying branched chain aliphatic acid in butter from yak |
| CN108774580A (en) * | 2018-06-20 | 2018-11-09 | 张建春 | The extracting method of unsaturated fatty acid in a kind of Chinese fiber crops seed |
| CN108774580B (en) * | 2018-06-20 | 2022-03-22 | 张建春 | Method for extracting unsaturated fatty acid from hemp seeds |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1712609A1 (en) | 2006-10-18 |
| JP2006291204A (en) | 2006-10-26 |
| US20060229461A1 (en) | 2006-10-12 |
| KR100539357B1 (en) | 2005-12-28 |
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